The present tutorial review reports on the synthetic approaches for the formation of "polyoxothiometalate" compounds with special emphasis on the unique reactivity of the preformed sulfur-containing cationic building blocks {Mo(2)O(2)S(2)}(2+) and {Mo(3)S(4)}(4+) toward polyoxometalate building blocks. Such simple chemical systems, based on chemical and structural complementarities between ionic reactive moieties have led to the synthesis of a series of relevant clusters with unrivalled large nuclearity structural arrangements, such as loops, triangles, squares and boxes. Specific reaction parameters and considerations will be pointed out showing that a deliberate pure inorganic supramolecular chemistry based on weak interactions, flexibility and dynamic is possible with polyoxometalates.